Process for the production of complex copper compounds of direct-dyeing dyestuffs onthe fiber



.plexes which-are in some degree stable.

United States Patent PROCESS .FOR THE PRODUCTION .OF COPPER COMPOUNDS OF DlRECT-DYEING DYESTUFFS ON THE FIBER Emil Kraehenbuehl, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland No Drawing. Application October 4, 1954 Serial No. 460,260

Claims priority, application Switzerland October 13, 1953 3 Claims. (Cl. 8-72) It is known that the properties of certain direct-dyeing dyestuffs, that is to say, dyestuffs which are absorbed substantively by cellulose fibers without the aid of mordants, can be improved by treatment on the fiber with an agent yielding copper. A great many dyestulfs are known, which, by virtue of their constitution, are capable of forming complex copper compounds, and among these dyestuffs there are especially important those which in the metal-free condition (that is to say, containing no heavy metal bound in complex union), possess a useful solubility in water, but of which the complex copper compounds are sparingly soluble or insoluble in water. With such dyestufis there are oftenobtained, after conversion on the fiber into the corresponding complex copper compounds, dyeings having especially valuable properties of fastness. Processes for dyeing with such dyestuffs are known in which there are carried out mom and the same bath first dyeing and then, advantageously the production of complex copper compounds of directdyeing metallizable dyestuffs on the fiber can be carried out with advantage ,by using. cuprous. thiocyanate as the agent yielding copper.

The copperthiocyanate can .be-prepared most simply by the reaction of a soluble cupricsalt with an alkali thiocyanate. When suitably prepared it is obtained directly in a rather finely powdered form. After being filt ed ofb sad antag ly u ed in the format an aqueous paste of known strength for the purposes of the present invention. v v p The treatment of the dyeings produced with directdyeing metallizable dyestuffs with copper thiocyanate may, if desired, be carried outin a fresh bath. It is, however, possible to carry out this treatment in the dycha hitself, esn c al y after the b thsha een ex n v ly exhausted. "It is-unnecessary to neutralize any alkaline reaction of the bath used. If desired, the reaction may be carried out in a neutral to acid medium.

For conversion into the corresponding complex copper compounds there are suitable in the present process all those dyestuffs which are capable of forming -,metal.,com-

However, there,

2 in complex union and which in the form of copper complexes are sufiiciently soluble in water to be used for dyeing according to the usual direct dyeing methods.

The present process is especially important'for producing-prints with metallizable direct-dyeing dyestufis. It is known to print on cellulose fabrics copper-free substantive dyestuffs which are capable of forming copper complexes with the addition of a solution promoter (caustic soda solution, urea), an electrolyte not having a salting out action (Na HPO and, if desired, a mild oxidizing agent (sodium 'nitrobenzene sulfonate) and a thickening, then to fix the dyestuff on the fiber my steaming, and,

-with or without intermediate rinsing, to render the print fast to washing by'after-treatment with a soluble copper salt with or Without the addition of a cation-active amineformaldehyde condensation product.

The latter process has found rather Wide application and has been used in many cases instead of theformer customary printing process with chrome mordant dyestuifsjbut it has the great disadvantage that after steaming, treatment in a bath containing a copper salt is necess ary, and this not only involves the risk of staining to a greater or less extent the white ground by the copper salt, but, what is still more undesirable, certain colors which are sensitive to copper undergo a change inshade and their properties of fastnessare affected.

Various attempts have been made to incorporate .a copper compound with printing colors containing adyestuff capable of being coppered, in order to avoid the subsequent after-treatment. It has-been found that the copper compounds hitherto proposed for this purpose are much too soluble and consequently form ,in the printing color at least partially the insoluble dyestuffrcopperscomplex which can be fixed on the fiber only to a very small extent. Consequently as compared with the method of after-treating the prints, printing colors madeeup in this mannerg'lve a markedly lower yield and have a poor stability.

It has been found that cuprous thiocyanate, which is yerysparing-ly soluble, is suitable :as an addition to printing colors containing direct dyestuffs capable of being coppered. Thus, printing compositions which conare used withadvantage thosedyestulfs which can be used in the metahfree condition in the usual manner for dye- 7 tain ametallizable direct-dyeing dyestufl andalso cuprous :at-hiocyanate possess a good stability without :the complex copper compound of the metallizable dyestufi being formed Such printing pastes may contain thensual thickening agents customary in printing with direct-dyeing dyestufiasuch ,as vegetable mucilages, starches, salts of cellulose-glycollic acid :and the like. In many cases it is of advantage to add a substancesapable of prompting solubility such as thiodiglycol or another polyhydric alcohol. The printing compositions may, if desired also con ain su an e o al a in a ti n. uch a sodiu hydroxide, sodium-carbonate, potassium carbonate, secondary or tertiary phosphates, disodium phosphate, trisodium phosphate,- sodium pyrophosphate or sodium polyphosphates,-' if such substances are necessary or desirable for dissolving the dyestuff. In such cases it may, however, be of advantage to reduce the strongly alkaline reaction by the addition of a butler substance, for example, an acid phosphate, or even to adjust the pH to a lower value by the addition of a suitable acid (acetic acid, formic acid or phosphoric acid).

Although, -as already stated, such printing compositions aresurprisingly stable at normal room temperatures up to 30 0., there occur, at a raised temperature, for example above C. but particularly under steaming conditions, on the one hand, fixation of the dyestuff ,on the fiber, and, on the other, the formation of the copper complex, so that the print generally has the fastness ofan after-coppered dyeing produced with the same dyestufis. It is possible to add a weak oxidizingagentto the printing composition, for example, sodium 3-nitro-, ,lizable y fi and f pl thiocyaflate SIISPQIISiOH benzene-l-sulfonate, but, surprisingly, this is not necessary and then steaming the lmpfegnated fiber wlth Without notwithstanding that the copper in the cuprous thiocyanate intermediate y On the fibers thus y Pflnts Call is present in monpvalent f be produced with the aid of similar dyestuffs or discharge It is frequently of advantage, to add a hydrotropic 5 Printing with h Ordinary reductive dischargfa Paste after agent, which accelerates fixation of: the dyestuff on the Steaming use of Cold folllard dyebafhs 15 0f P fiber, for example, thiodiglycol, which has been mentioned lar advantage In that the rate of absorption of most y above another glycol derivative, but more especially baths is greatly reduced, which results in obtaining more urea. expedient accelerates the fixation of the dyeeasily dyeings which are uniform from end to find when stufi on the fiber, which in some cases would otherwise Combining Several dyestuffs, and p g a Shade invarinsufiiciently rapid. In ome a th properties f iable through a whole dyeing batch with less difficulty.

wet fastness of the prints can be still further improved The following pl illustrate the invention, the p by after treatment of the f finished print with a cation- Parts and Percentages being y Weight! active amine-formaldehyde condensation product, Example 1 The present-process may also be combined in a suitable mannenwith another dyeing or printing process, especially in producing prints of which the patterns are separate from'o ne another? Thus, for example, cellulose-containing fabrics, can be printed in one operation,

Printing compositions are prepared in accordance with the recipes I to IV,'and each of them is used for printing a fabric of cotton, or artificial silk or staple fibers of regenerated cellulose.

advantageously. in aroller printing machine having two or more printing rollers, a part of which carry a print- I H III IV ing composition :in accordance with the present inven- P tion, and another part a printing composition of a difi s if; ferent kind, and the printed material finished in a suit- $32 5 able manner. Valuable results are obtained, for example, I by first impregnating the material to be printed with gggggf f 'fifihgbfbggffi 5 10 suitable coupling componentsfree from water solubiliz- (neutra zed with sodium y 350 t; groups (so-callednaphthols. especially y y- Mfiiaaaanrasragsrsrjj:3:: .ffl 3 12 3 naphthalene-3-carboxylic acid arylamides), and then cupmushthmyamto paste of 50 35 pn'nting,,on the one hand, with a printing paste con- Tl liiliiigi i:IIIIIIIIII" taininga direct-dyeing metallizable dyestuff in accord- DiSOdm-m -f ance with the present process and, on the other, with a so-calledkbase printing composition viz. a printing compositioncontaining a diazo compound suitable for the 35 For preparing the above printing compositions the production of ice colors. As is known, these dyestufis following dyestufis are used:

produced, for example, directly on the fiber in base Printing composition l.-The dyesuff of the formula 1 H038 (I) OH:

no N: NH-C O-IINQ-N: Qon (yellow) 1100 H. OOH printing are distinguished by very good properties of Printing composition Il.--The dyesufl of the formula on: orl=on N-N on=on N--N N=N on Q Q Q Q Q om 0H 0-H 0.11 0011 t (orange wet fastness. Moreover,these two classes of dyestutis ex- Printing composition lll.-The dyestufi of the formula 0011. HO; NH-CO-HN SO H 00H, (blue) n00 on, n H on, OOH tend the range of tints available in an advantageous man- Printing composition lV.--The dyeaufl of the formula 5 O NH;

MN MQOH (m, V

oorr act, so that their joint use in the manner described above The prints are dried, steamed twice for 8 minutes in a leadsto a valuable enrichment of the possibilities hither- Mather-Flatt apparatus, rinsed for 10 minutes in running to available for producing printshaving good properties Water, soaped for 5 minutes at 40 C. with a solution of wet fastness. 1 p which contains 5 grams of soap and 2 grams of anhydrous Byflthe present process not only prints, but, as stated sodium carbonate in 1 liter of water, again rinsed and above, also dyeings can be produced. dried.

, Thus, for example, particularly valuable results are The more strict requirements with regard to fastness Ob ined by impregnating cellulosic fibers on a foulard to washing which are not sufiicient in the case of prints cold ,dyeing liquids containing thedissolved metalobtained with printing composition IV can be met by sat en 5 substantially improving the fastness to washing by an The followingdyestufis are used for preparing "the after-treatment, following the first rinsing, with a cationprinting-"compositions I to III: p active amine-formaldehyde condensation product at room Printing com position I. 'I 'he'-dyestulf of the formula HOaS OHs l v. Q, I

H H36 7 l V "coon temperature. In the other cases the fastness to washing Printing composition II. The 'dyest'ufi of the formula H00 7 Y i is also markedly improved by such an after-treatment,

Rol s C| CHa HO HlII- HOOC H H038 and it is generally recommended in the case of dark The prints a're' dried, steamed twicefor'8'minutes in a tints. Mather-Plattapparatus, soapedfor 5 minutes at 90 C. Example 2 with a solution which contains, in 'l literof water, 5 l grams of soap and 2 grams of-anhydrous" sodium car- Prmtmswmposltlons ar -p p m accordance Wlth bonate, rinsed in the cold and dried; There'a're' obtained the YBCIPES I to H1 Elven the cottfm in this ma nn'er' 2-c'olor p'rints whi'ch'are'fast to washing, fabric is impregnated wlth an alkalln'esolutlon WhlCh the f b i b i i d -th a 'h d, :the i of l' 12 f 0f Y Y P f Y one of the above dyestuffs and, on the other, a scarlet acld PhenY1am1de 1I1 1 11161 of Water allld then dfled- The tint with the use of diazotized l-amino-ZzS-dichlor'cibenimpregnated fabr1c'istheneprlnted with two rollers one izeneland a red timvwith theme f diazotized, p 1 -2- of which applies one of the printingvcompositions I to III methoxydwhlombenzene, and the other of which applies a printing paste prepared l in the'usual manner and containing diazotized l-aminol 2:5-dichlorobenzene or diazotized 1'-amino-2-methoxy-5-. 40 A dyebath is prepared from 4000 parts of, Water, 2 chlorobenzene, the two rollers printing separate vpatterns parts ofsodium carbonate, 30 parts of crystalline sodium on the fabric. 7 Y sulfate and also 1.2v parts of one 'ofthefdyestufis used for preparing 'the printing. compositions I, II and III in Ex- Examplc 3 I H In ample 2, and 100' parts of cotton are entered at 40 C.

The temperature is raised to 95 C., and dyeing is car- Parts Parts ried on for 1 /2 hours at that temperature. The dyebath 13 20 is then cooled to 70 C., and there is then added 0.8 part Water of cuprous thiocyanate in the form of a paste of 5% s odlum htildroxide soluftionof30%gtrength 1 20 10 5 strength. The temperature is slowly raised to 90 C., i e ri i t h 550 525 500 and the bath for 14 at h tempera Monoammom'urn phosphate 24 12 ture. The dyeing is then rinsed and finlshed 1n the usual Cnprous thiocyanate paste of 50% strength... 35 35 35 Thiodiglycol 50 manner- Formic acid of 85% strength 10 10 10 Ex l 4 g 1,000 1,000 1,000 For preparing the dyebath one of the following dyestulfs is used:

I H0 5 OCHa HO N=N NH-OC-Q H0O Ha NH-C 0HN- N=N OH yellow 1 part II OOH H0 8 0on3 N=N- N= NH-O CGN=N OH orange 1.43 parts H3 H3 7 OOH 0311 III on HO OH' H(') -N=N N=N blue a 7 :Thelgiyen quantity of dyestufi is dissolved'in 1000 parts of. boiling water andthe solution then cooled to .10-15? Ct?i parts. otcuprousthiocyanate are added to the cold solution and the whole is well mixed. Then on a foulard having two rollers, a cotton, cellulosic or viscose fabric impregnated in such a way that the fabric absorbs 90 percentof the liquidtcalculatedon the weight of the fabric; The impregnated fabric is then treated accordingto one of thefollowing methods;

(a) The fab "c" eamed for 8.m1nutes In a Mather- Platt apparatus at about 105? C., then washed for half an hour at 50 C. witl1 a solution which contains 5 parts of p heptadecyl N bcnzylbenzimidazol sodiumdisulfonate in '1000parts of water and then rinsed and dried.

(b) The fabric is first dried,.then steamed for 8 minutes'in a'Mather-Platt apparatus at about 105 C. and

then washed as described under (a), rinsed and dried.

(c) The fabricis dliedg j p After being treated according to (a), (b) or (c) the fabric is printed with. a discharge paste having the followingcomposition:

150 parts ofsodiumformaldehyde sulphoxylate 400 parts of crystal gum thickening l 100 ,partsof :calcium salt of disulphonic acid of dimethylphenyl-benzyl-ammonium.chloride A t 170 partsofwater U a I 100 partsof potassium carbonate 50. parts of glycerine 30 parts of: an aqueous suspension of anthraquinone of 30 percent strength 1000 parts T v s, After printing, the fabric is dried, steamed for 8 minutes in a Mather-Flatt apparatus, rinsed for 15 minutes with coldtwater, after-treated for 10 minutes in a bathcontainingj parts by volume of concentrated ammonia b11000 parts of water, rinsed cold, soaped at 40 C. in a solution containing 3 parts of soap and 1 part of anhydrous sodium carbonate in 1000 parts of water, rinsed cold once more and finally dried. Depending on the choice of dyestuff (see above) there are obtained stuff of which the complex copper compound is sparingly soluble to insoluble in water and containing cuprous thiocyanate.

2. A process for producing complex copper compounds of direct-dyeing metallizable azo dyestuifs on the fiber, whichcomprises printing cellulosic fibers, which have been impregnated with a coupling component free from water-solubilizing groups, on the one hand with a printing paste containing a diazo compound suitable for the ;production of ice colors, and on the other hand with a printing paste containing a direct-dyeing metallizable azo dyestuflf of which the complex copper compound is sparingly soluble to insoluble in water and containing cuprous thiocyanate. 3. A printing paste for producing complex copper com- I pounds of direct-dyeing metallizable azo dyestuffs on cellulose fibers, which paste contains a direct-dyeing metallizable azo dyestuff, of .which the complex copper compound is sparingly soluble to insoluble in water, and also contains cuprous thiocyanate.

' References Cited in the file of this patent UNITED STATES PATENTS Straub Feb. 28, 1939 OTHER REFERENCES Principles and Practice of Textile Printing by Knecht and Fothergill, 3rd ed., 1936, published London by Charles Gritfin & Co., pp. 237, 238.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2,8 0,444 June. 24, 95

Emil Kraehenbuehl It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 12, for "my" read ea by column 8, line 6, after "dyestuffs" insert fast a Signed and sealed this 9th da; of December 1958a SEAL A ttest:

KARL H; .AXLINE ROBERT C. WATSON Commissioner of Patents Attest ing Oflicer 

1. A PROCESS FOR PRODUCING COMPLEX COPPER COMPOUNDS OF DIRECT-DYEING METALLIZABLE AZO DYESTUFFS ON THE FIBER, WHICH COMPRISES PRINTING CELLULOSIC FIBERS WITH A PRINTING PASTE CONTAINING A DIRECT-DYEING METALLIZABLE AZO DYESTUFF OF WHICH THE COMPLEX COPPER COMPOUND IS SPARINGLY SOLUBLE TO INSOLUBLE IN WATER AND CONTAINING CUPROUS THIOCYANATE. 